Hybrid solid-state cell with a sealed anode structure

ABSTRACT

A monolithic ceramic electrochemical cell housing is provided. The housing includes two or more electrochemical sub cell housings. Each of the electrochemical sub cell housing includes an anode receptive space, a cathode receptive space, a separator between the anode receptive space and the cathode receptive space, and integrated electron conductive circuits. A first integrated electron conductive circuit is configured as an anode current collector within the anode receptive space. A second integrated electron conductive circuit is disposed as a cathode current collector within the cathode receptive space.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation application of U.S. patentapplication Ser. No. 16/898,126 entitled “Hybrid Solid-State Cell with aSealed Anode Structure,” filed Jun. 10, 2020, which is acontinuation-in-part application of U.S. patent application Ser. No.16/702,417 entitled “Hybrid Solid-State Cell with a Sealed AnodeStructure,” filed Dec. 3, 2019, which is a divisional application ofU.S. patent application Ser. No. 16/262,058 entitled “Hybrid Solid-StateCell with a Sealed Anode Structure,” filed Jan. 30, 2019, now U.S. Pat.No. 10,535,900, which claims priority to U.S. Provisional ApplicationNo. 62/624,476 entitled “HYBRID SOLID-STATE CELL”, filed Jan. 31, 2018,the contents of which are incorporated by reference in its entirety.

The present application is also related to U.S. patent application Ser.No. 15/883,698, entitled “CERAMIC LITHIUM RETENTION DEVICE,” filed Jan.30, 2018, the disclosure of which is hereby incorporated herein byreference in its entirety.

FIELD OF THE INVENTION

The present invention relates to a monolithic ceramic electrochemicalcell housing and associated methods of manufacturing.

BACKGROUND

Lithium ion batteries (LIBs) provide significant improvements in energydensity and cost per watt hour compared to the NiCad and Lithium metalhydride cells that preceded them. Notwithstanding, the manufacturingcosts to produce a LIB is cost prohibitive in electric vehicles.Furthermore, the low energy density causes our electronic gadgets to belarger and bulkier than desirable. Recent improvements in the field haveattempted to address these drawbacks by increasing the density ofsolid-state cells.

While cells with lithium metal anodes provide superior energy density,rechargeable cells cannot be constructed with lithium metal anodesbecause of the risk of dendrite formation during the charge cycle. Thedendrite formation during the charge cycle results in short circuitsthat cause explosion and combustion during ignition of the liquidelectrolyte. The liquid electrolyte is a highly combustible organicsolvent and does prevent dendrite growth between the anode and cathode.As a result, LIBs are typically made up of intercalation anodes, whichallow lithium ions to be inserted into the crystalline structure ratherthan being plated onto a current collector. Inserting the lithium ionsinto the crystalline structure reduces the effective energy storagecapacity of the anode to less than 10% the theoretical capacity oflithium metal.

Liquid electrolyte also limits a maximum voltage for the battery.Typical liquid electrolytes decompose above four-volts differencebetween an anode and a cathode, which effectively limits the maximumopen circuit voltage of LIBs to about 3.8-volts. Cathode materials thatcan produce 6 volts against a lithium anode are considered practical,but not usable in cells with liquid electrolyte. The ability to use suchhigh voltage cathodes could increase the energy density of the cells by50%.

An obvious solution is to use a nonflammable electrolyte that resistsdendrite formation, is unaffected by potentials above 6 volts, andpossesses ionic conductivities equaling or approaching those of theliquid electrolytes. While ceramics with high lithium ion conductivitiesmeet those requirements, they also have physical and chemical propertiesthat prevent practical implementations. For example, ceramic materialsare typically very rigid and brittle. Furthermore, a practical cell ismade up of stacks of sub cells, each in turn includes very thin layersof the basic components of an electrochemical cell. Common approachesinclude constructing a cell by producing the thin layers (<40 μm for theseparator) in sheets and assembling them in order. However, the thinlayers are fragile and rarely flat, causing a discontinuous contactbetween individual layers across the meeting surfaces. Applying pressureto the stack of layers tends to improve the contact, but unacceptablyincreases the risk of fracturing a layer.

Moreover, applying pressure to the stack of layers fails to create anintegrated connection between layers, rather it creates pressure contactbetween two surfaces. Typical battery materials are chemically activecausing the contact to react with the surrounding environment. In otherwords, surface contacts, even between like materials, will besusceptible to increased ionic and/or electrical resistance at thepoints of contacts.

Other drawbacks associated with a cell with lithium metal anode includesa difficulty in achieving a true hermetic seal around the anode space.Any oxygen or water ingress into the anode space will cause oxidation ofthe lithium, so a non-hermetic seal reduces the capacity and eventuallydestroys the cell as oxygen or water leak into the cell. Although, it isclear liquid electrolyte poses significant drawbacks, liquid electrolyteis able to flow into any open space where a lithium atom was oxidized toa lithium ion and moves across the separator to the cathode, to maintainthe ionic conductivity throughout the cell. Ceramic electrolyte does notpossess this ability. As a result, the conventional approach to usingceramic electrolyte is to create a planar interface between the lithiummetal and the ceramic cathode. In this way, only a thin layer of lithiumclose to the ceramic electrolyte can oxidize and move into theelectrolyte. The result is a very big limitation to the energy storagecapacity of the anode. Thin film solid-state cells epitomize thisdrawback because the useable thickness of the lithium metal anode isonly a fraction of the metal deposited.

There is a need to address the short comings of current solid-state celldevelopment efforts.

SUMMARY

A monolithic ceramic electrochemical cell housing is provided. Thehousing includes two or more electrochemical sub cell housings. Each ofthe electrochemical sub cell housing includes an anode receptive space,a cathode receptive space, a separator between the anode receptive spaceand the cathode receptive space, and integrated electron conductivecircuits. A first integrated electron conductive circuit is configuredas an anode current collector within the anode receptive space. A secondintegrated electron conductive circuit is disposed as a cathode currentcollector within the cathode receptive space.

In some embodiments, the anode receptive spaces are configured ashermetically sealed volumes, partially filled with strands ofsolid-state electrolyte material. The solid-state electrolyte materialincludes a high-density ceramic. The high-density ceramic can beselected from a group consisting of: sulfides, borides, carbides,nitrides, phosphides, oxides, selinides, florides, chlorides, bromides,iodides, or combinations thereof. The strands of solid-state electrolytecan form a network of continuous ionic conductivity between theseparator and the anode current collector.

The strands of electrolyte can occupy between 20% and 80% volume of theanode receptive spaces. The anode current collector can serve as currentcollector for the anode receptive spaces of the electrochemical sub cellhousing and second anode receptive spaces of a second adjacentelectrochemical sub cell housing.

The cathode receptive spaces can be partially filled with strands ofceramic material between 1% and 60% volume. In another embodiment, thecathode receptive spaces can be devoid of ceramic electrolyte material.The monolithic ceramic electrochemical cell housing can also includeinsulating material between each of the electrochemical sub cellhousing.

The cathode layer can include a seal structure in a filling apertureconfigured to contain catholyte. The seal structure can be configured toisolate the catholyte and provide pressure relief from the cathodereceptive spaces. The anode receptive spaces can be filled with anodeactive material during an initial charging phase.

The anode receptive spaces can be sealed and the cathode receptivespaces can be partially sealed. The monolithic ceramic electrochemicalcell housing can also include an anode electrical contact connectinganode sub-cell current collectors and a cathode electrical contactconnecting cathode sub-cell current collectors.

A manufacturing method for assembling a monolithic ceramicelectrochemical cell housing is also provided. The method can includedepositing precursor materials in a flexible format to form amulti-layer structure. The method can also include heating themulti-layer structure to convert the precursors into a single monolithicstructure void of physical interfaces between deposited layers. In someembodiments, the format is fluid, selected from a group consisting ofpastes, flowable powders and green tapes. In some embodiments, theprecursors are deposited using additive manufacturing techniques.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to describe the manner in which the above-recited disclosureand its advantages and features can be obtained, a more particulardescription of the principles described above will be rendered byreference to specific examples illustrated in the appended drawings.These drawings depict only example aspects of the disclosure, and aretherefore not to be considered as limiting of its scope. Theseprinciples are described and explained with additional specificity anddetail through the use of the following drawings.

FIG. 1 illustrates an exemplary solid-state cell, in accordance with anembodiment of the disclosure;

FIG. 2 illustrates an integrated framework of the exemplary solid-statecell of FIG. 1, in accordance with an embodiment of the disclosure;

FIG. 3 illustrates a sub-cell housing, in accordance with an embodimentof the disclosure,

FIG. 4 illustrates a sub-cell housing, in accordance with an embodimentof the disclosure;

FIG. 5 illustrates a sub-cell housing, in accordance with an embodimentof the disclosure;

FIG. 6 is a flow chart illustrating manufacturing method of a sub-cellhousing, in accordance with an embodiment of the disclosure;

FIG. 7 illustrates an alternate integrated framework of the exemplarysolid-state cell of FIG. 1, in accordance with an embodiment of thedisclosure;

FIG. 8 illustrates an anode layer of the exemplary solid-state cell ofFIG. 1, in accordance with an embodiment of the disclosure;

FIG. 9 illustrates a cathode layer of the exemplary solid-state cell ofFIG. 1, in accordance with an embodiment of the disclosure;

FIG. 10 illustrates a cell schematic of the exemplary solid-state cellof FIG. 1, in accordance with an embodiment of the disclosure; and

FIG. 11 illustrates a cell schematic of the exemplary solid-state cellof FIG. 1, in accordance with an embodiment of the disclosure.

DETAILED DESCRIPTION

The present invention is described with reference to the attachedfigures, where like reference numerals are used throughout the figuresto designate similar or equivalent elements. The figures are not drawnto scale, and they are provided merely to illustrate the instantinvention. Several aspects of the invention are described below withreference to example applications for illustration. It should beunderstood that numerous specific details, relationships, and methodsare set forth to provide a full understanding of the invention. Onehaving ordinary skill in the relevant art, however, will readilyrecognize that the invention can be practiced without one or more of thespecific details, or with other methods. In other instances, well-knownstructures or operations are not shown in detail to avoid obscuring theinvention. The present invention is not limited by the illustratedordering of acts or events, as some acts may occur in different ordersand/or concurrently with other acts or events. Furthermore, not allillustrated acts or events are required to implement a methodology inaccordance with the present invention.

In view of the foregoing, embodiments disclosed herein are directed toan apparatus and a manufacturing process for producing a monolithicceramic electrochemical cell housing. The monolithic ceramicelectrochemical cell housings are produced at a per watt costs belowcurrent lithium ion batteries (LIBs). The volumetric energy densitiesare significantly higher than current LIBs, and in capacities rangingfrom a few milliwatt hours to kilowatt hours. In some embodiments,multi-material additive processes are incorporated to assemble the cellsfrom precursors of the final materials, and convert the precursors totheir final properties when the assembly is complete. Thesemulti-material additive processes are implemented to eliminate thedrawbacks of assembling cells from ceramic sheets with their finalproperties. The precursors can be in a fluid or plastically deformablesheet state, which can be layered and bonded together as precursors. Theprecursors in this state are also easy to handle and form into thedesired configuration.

As a result, after the conversion to the final properties the resultingstructure is a monolithic block with no discernable interface whereadjacent layers were joined. The interface of the layers of dissimilarprecursor materials is designed chemically and physically to optimizethe conductivity between the two final materials. Specifically, a truechemical bond can be formed at the interface, avoiding the possibilityof uncontrolled reactions with the environment or incomplete contactbetween materials will compromise the desired properties of theinterface. Conversion of the precursors in some embodiments include heattreatment processes that remove organic material components of theprecursors, convert the remaining constituents to the final desiredchemistry, and sinter the final materials to their respective densitytargets.

The disclosed multi-material additive processes also produce a designthat allows the liquid electrolyte to maintain ionic conductivitycompletely across an electrode space regardless of the state of charge.For examples, a porous structure of electrolyte can be created across ananode space, which forms a fully interconnected web of ionic conductivematerial from the solid electrolyte separator to the current collectorof the electrode. The porous structure can be configured such that thedistance between adjacent portions of the ionically conductive web isless than two-times the maximum distance an ion can be transferred intothe ionically conductive electrolyte.

The disclosed multi-material additive processes also provide acost-effective configuration of a hybrid cell design that incorporates acathode with a similar composition to the typical cathodes employed inconventional lithium ion cells, and an anode that it is a hermeticallysealed space. Specifically, the anode can be bounded by the currentcollector on one side, the separator on the opposite side, filled withthe ionically conductive porous structure, and void of any intercalationhost or active charge transfer species immediately following manufactureof the cell structure. The active charge transfer species (e.g.,lithium) can be introduced to the anode space by plating lithium fromthe cathode to the anode current collector during the conditioning, orfirst charging of the cell.

FIG. 1 illustrates an exemplary solid-state cell 100 in accordance withan embodiment of the disclosure. The general structure of thesolid-state cell 100 can include a monolithic and highly integratedframework 102, as illustrated in FIG. 2. The integrated framework 102can include one to thousands of stacked sub cells housings 80.

Referring to FIG. 2, each sub-cell housing 80, with alternating thinlayers, can include an anode receptive space 41 and a cathode receptivespace 11. The anode receptive space 41 and cathode receptive space 11can be separated by a thin separator 30, which may be made up ofsolid-state electrolyte. Each anode receptive space 41 can be made up ofa hermetically sealed, defined volume, partially filled with strands ofsolid-state electrolyte material (shown in FIG. 3 as 32).

Referring to FIG. 3, the hermetically sealed, defined volume, partiallyfilled with strands of solid-state electrolyte material 32 form a regionof controlled porosity (referred to herein as the “empty space 42”). Thesolid-state electrolyte material 32 can include a high-density ceramic.For the purposes of this example, the high-density ceramic can include,but is not limited to, sulfides, borides, carbides, nitrides,phosphides, oxides, selinides, florides, chlorides, bromides, iodides,or combinations of thereof. The high-density ceramic can include anyceramic that exhibits room temperature conductivities of the intendedcharge transfer ion of the specific battery design, greater than 1×10⁻⁶S/cm. In some embodiments, the charge transfer ion is Li⁺. Inalternative embodiments, the charge transfer ion can be either Na⁺, Mg⁺,K⁺, and Al⁺³.

The strands of solid-state electrolyte 32 can form a network ofcontinuous ionic conductivity between the separator 30 and the anodecurrent collector 50. The porous electrolyte structure can be made fromsolid-state electrolyte material, similar to the separator 30, but witha controlled structure. Continuous strands of electrolyte can besurrounded by the empty space 42 and extend from the separator 30 andthe current collector 50. The empty space 42 can also extend from theseparator 30 to the anode current collector 50. In some embodiments, thestrands of electrolyte can occupy between 20% and 80% of the volume ofthe anode receptive space 41 (also shown in FIG. 2) while the void spaceoccupies the remaining volume. In some embodiments, the porous structureis designed such that the average distance between adjacent strands ofelectrolyte material can be between 0.000001 mm and 0.040 mm. Referringback to FIG. 2, the anode receptive spaces 41 for two adjacent sub cellhousings 80 can be juxtaposed, separated by the current collector 50.The current collector 50 can serve as current collector for both anodereceptive spaces 41 of the two adjacent sub cell housings 80.

Each cathode receptive space 11 can also be a defined volume partiallyfilled with strands of ceramic material. In some embodiments, thecathode receptive space 11 can form a region of controlled porosity. Inother embodiments, the cathode receptive space 11 can be an open definedvolume free of any ceramic material. In some embodiments, strands ofelectrolyte material in the cathode receptive space 11 can occupy from0% to 60% of the total volume. Furthermore, the strands of electrolytematerial can be designed such that the average distance between adjacentstrands of electrolyte material can be between 0.02 mm and 200 mm.

The strands of ceramic material can include solid state electrolytematerial that provides ionic conductivity across the thickness of thecathode space similar to the porous structure in the anode receptivespace 41. Alternatively, the ceramic strands can be provided asmechanical elements to control the precise thickness of the cathodereceptive space 11.

In some embodiments, the cathode receptive spaces 11 of two adjacent subcell housings 80 can be configured such that one cathode receptive spaceserves said two adjacent sub cell housings 80. Referring momentarily tothe cathode current collectors 20 in FIG. 2 and FIG. 11. Each of the twoadjacent sub cells can be configured with an electron conductive layerdirectly on the cathode side of the separators 30. The cathode receptivespace 11 (shown in FIG. 11) of the two sub cell housings can be boundedon either side by cathode current collectors 20 of the two adjacent cellhousings. The distance between the separators 30 of the two adjacent subcell housings can be calculated to create a cathode receptive space 11volume that includes an amount of catholyte that meets the designparameters of the two adjacent sub cells.

With reference to FIGS. 2 and 11, a cathode current collector 20 of asub-cell 80 may be positioned in direct contact with a surface of asub-cell separator 30, opposite the surface defining one surface of thesub-cell anode receptive space 41, thus defining one boundary of cathodereceptive space 11. Two adjacent sub-cells 80 may be juxtaposed incontact, cathode receptive space 11 to cathode receptive space 11, withcurrent collectors for each of the two cathode receptive spaces 11positioned in contact with the cathode side of the separator 30 of therespective sub-cell 80. The resulting cathode receptive space 11 maythus be a volume sufficient to contain cathode material for twosub-cells 80 and the major surfaces of cathode receptive space 11defined by the current collectors 20 of the two adjacent sub-cells. Theadvantages of this arrangement are that two very thin current collectors20 supported on a separator 30 can occupy less volume than a singleunsupported current collector positioned to separate two cathodereceptive spaces 11. Secondly, positioning the current collectors at theperiphery of a cathode receptive space creates a single double thickcathode receptive space, facilitating easier insertion of the cathodematerial into the cathode receptive space 11.

The cathode current collectors 20 may be comprised of a metal or a metalalloy or a conductive ceramic, or a conductive carbon based material.Cathode current collectors 20 may be further comprised of an ionconducting material chosen to conduct the intended charge transfer ionof the specific battery design. The ion conducting material of thecathode current collectors 20 may be the same solid-state electrolyte ascomprises the anode receptive space 41 and the separator 30. In oneembodiment, the ion conducting material is lithium lanthanum zirconate.The metal or metal alloy or conductive ceramic or conductingcarbon-based material of the cathode current collectors 20 may comprisea porous film that forms an electronic percolating network through theplane of cathode current collector 20. The metal or metal alloy orconductive ceramic or conducting carbon based material of the cathodecurrent collectors 20 may comprise any value or values between 20% and99% by volume of the cathode current collector 20. In some embodiments,a current collector 20 may be present on only one side of cathodereceptive space 11.

Referring back to FIG. 2, the cathode receptive space 11 can be furtherdefined by low porosity ceramic walls 46 extending between theseparators 30 to create a seal between the separators 30. The ceramicwalls (shown in FIG. 9 as 46) can extend around at least 60% of theperiphery of the cathode receptive space 11. The low porosity ceramiccan be made up of solid-state electrolyte.

With reference to FIG. 7, in some embodiments, each sub-cell housing 80can be separated from surrounding sub-cell housings 80 by layers ofinsulating material 25. The insulating material can be disposed betweenthe separators of adjacent sub cell housings, at a calculated distance.The distance can be calculated to create cathode receptive space 11volume and anode receptive space 41 volume to contain an amount ofcatholyte and charge transfer species. The amount of catholyte andcharge transfer species are designed to meet the configurationparameters of the sub-cell 80. In these embodiments, current collectorscan be disposed on the surfaces of the layer of insulating material 25or anywhere within the cathode receptive space 11.

FIG. 3 illustrates a sub-cell housing 80, in accordance with anembodiment of the disclosure. Each sub-cell housing 80 is a layeredstructure, which can include solid-state electrolyte with alternatinglayers of high density electrolyte material. The sub-cell housing 80also can include layers with a high degree of controlled porosity. Thelayers include anode layers 44, cathode layers 10, and separator layers30. The anode and cathode layers can be made up of high porosity whilethe separator layers can be made up of high density electrolyte. Theanode layers 44 can include anode receptive spaces 41, low porosityboarders 60 (Shown in FIG. 8), and anode current collectors 50. Thecathode layers 10 can be made up of cathode receptive space 11, lowporosity boarder 46 and a filling aperture 49 (shown in FIG. 9). The lowporosity border 46 can be made up of high density ceramic material. Insome embodiments, the high density ceramic material can includesolid-state electrolyte. The low porosity border 60 completely andhermetically seals the anode receptive spaces 41 from the environment.The low porosity border 46 can also partially surround the cathodereceptive spaces 11, physically isolating the cathode receptive spacefrom other layers in the sub-cell housing.

Referring back to FIG. 3, the separators 30 are configured to separatethe anode receptive space 41 of each sub-cell housing from the cathodereceptive space 11 of each sub-cell to eliminate contact between thespaces. The separator layer 30 can be configured with a precisethickness to ensure it is void of open pores. In a preferred embodiment,the thickness of the separator layer can be range between 0.00001 mm to1.0 mm. The thickness of the anode receptive space 41 and cathodereceptive space 11 can be configured to optimize the performance of thespecific materials. The configuration of the open volume and thesolid-state electrolyte strands are also designed to optimize theperformance of the specific materials.

As indicated above, the cathode layers 10 can include cathode receptivespace 11 partially or completely filled with catholyte. The low porosityceramic walls can be positioned around at least a portion of the cathodereceptive space 11 and the cathode current collectors 20 within thecathode receptive space.

The cathode layer 10 can also include a seal structure in a fillingaperture 49 (shown in FIG. 2 and FIG. 9) configured to contain thecatholyte. The seal structure can be configured to protect the catholytefrom the environment and provide pressure relief from the cathodereceptive space 11. The separator layer 30 can include electricallyinsulated ceramic material. In some embodiments, at least a centralportion of the electrically insulated ceramic material includessolid-state electrolyte appropriate for the design charge transferspecies of the sub-cell. The low porosity ceramic walls can also includesolid-state electrolyte material and serve as protective packaging forthe sub-cell.

In a preferred embodiment, the multilayered structure of anode receptivespace 41, the cathode receptive space 11, the separators 30 and thecurrent collectors 50 and 20 can be assembled without either catholyteor anode active materials present. The catholyte material can beinserted through the filling aperture 49 (shown in FIG. 2 and FIG. 9)and sealed in place in the cathode layer 10. The catholyte material canbe made up of cathode active material, an electrolyte for the chargetransfer ion of the sub-cell, and an electron conducting material. Theelectron conducting material can include carbon, a metal or an electronconductive ceramic. The cathode active material can be made up of anintercalation host material suitable for the charge transfer ion.

Referring specifically to FIG. 5, the empty space 42 of the porous anodereceptive space 41 can be partially filled with anode active material 43during the initial charging of the battery. In some embodiments, theanode active material 43 can include lithium metal. The anode activematerial can be electro plated onto the anode current collector toinitiate the filling of the anode receptive space 41. The anode activematerial can then be electro plated onto the previously plated anodeactive material until the anode receptive space 41 fills with the anodeactive material 43.

The catholyte material can be inserted in the cathode receptive space 10by converting the catholyte material to a fluid and drawing the fluidmaterial into the porous structure under vacuum force. In someembodiments, converting the catholyte materials to a fluid can includemelting the catholyte materials, compounding the catholyte materialsinto a mixture of solid and liquid materials, dissolving the catholytematerials in a solvent, or converting the catholyte materials to a finepowder. In an alternative embodiment, the catholyte material can beconfigured as solid or semi solid structure. The structure can be shapedto precisely fit the cathode receptive spaces. In this embodiment, thecatholyte material structures can directly inserted and secured in therespective cathode receptive spaces.

The sub-cell can be configured to enable the introduction of thecatholyte material into the cathode receptive spaces, without damagingthe rest of the structure. For example, the sub-cell can be configuredsuch that all cathode receptive spaces are sealed continuously along atleast three quarters of the edges of the sheet like volume, by lowporosity ceramic walls 46. In some embodiments, the cathode receptivespaces are open from over 1/1,000 to ½ of the total circumference. Insome embodiments, the cathode receptive spaces are open at a firstlocation of the stack of cell layers. The first location enables thefilling aperture of the cathode receptive spaces to be immersed into afluid catholyte material. In some embodiments, the filling aperture canbe fully immersed in the fluid catholyte material.

Further, the sub-cell includes an anode electrical contact 92 of FIG. 10and FIG. 11, connecting all of the anode sub cell current collectors.The anode electrical contact can include an extension for makingelectrical contact on the outside of the sub-cell. The sub-cell alsoincludes a cathode electrical contact 94 of FIG. 10 and FIG. 11,connecting all of the cathode sub cell current collectors. The cathodeelectrical contact can also include an extension accessible for makingelectrical contact on the outside of the sub-cell.

In some embodiments, the electrolyte structure is the basic frameworkand exoskeleton of the solid-state cell 100. A continuous electrolyte isrequired within the anode region to transport lithium ions to and fromelectron conductive sites. The solid-state electrolyte can also serve asthe separator 30 between anode and cathode regions, as a fully denseceramic structure preventing growth of lithium dendrites during a cellcharging cycle. In the anode and cathode regions, the electrolyte canform a porous structure that emulates a liquid electrolyte, allowing iontransfer throughout the three-dimensional space regardless of the stateof charge. The electrolyte structure can seal the edges of the electroderegions, effectively completing a package around the sub-cell. Theresult is a structure of alternating dense and porous layers, integratedas a continuous structure throughout the cell with no apparentdiscontinuity at the interface of layers of similar material. Atinterfaces of chemically dissimilar materials, properties of thedissimilar materials are configured such that the only discontinuity atsuch interfaces is in the chemical composition of the interfacinglayers.

In some embodiments, assembly of the solid-state cell structure isaccomplished by sequential deposition of layers or partial layers. Thedeposition of layers or partial layers can be patterned appropriatelyfor the function of the individual layers, as precursors of the desiredfinal materials. The precursors include mixtures of materials that formdesired high density and electrochemical properties after a heattreatment. The mixture of materials can also act to bind the precursormaterials in the predetermined configuration. The binding materials canbe separate materials from those that form the desired end material. Inthis case, the binding materials are removed from the structure duringthe heat-treating process. In other embodiments, the binding materialscan form the desired end material and have binding properties.

FIG. 6 is a flow chart illustrating the manufacturing process of asub-cell housing. At step 601, the precursor materials are deposited informats which are highly flexible and not brittle. For example, theprecursor materials can be deposited as a fluid, including sheets whichare easily plastically deformed without sacrificing the integrity of thesheet. The fluids can include pastes, flowable powders and green tapes.It should be understood that the precursors can be deposited in oneformat or a combination of two or more formats. After all the layers ofthe cell structure are deposited, the completed structure can be heattreated to convert the precursors to the desired physical andelectrochemical properties at Step 602. Furthermore, the heat treatmentcreates a single monolithic structure with no physical interfacesbetween the deposited layers.

In some embodiments, the precursors can be deposited using additivemanufacturing techniques. For example, the precursors can be depositedusing a three-dimensional (3D) printer accompanied by a computer systemand guided by CAD data for each layer of the structure. In alternativeembodiments, the precursors can be deposited as layers of green(unfired) tape, prepared to the desired patterns, stacked in the designorder and laminated together. In alternative embodiments, both 3Dprinting and laminated tape deposition processes can be incorporated toform the complete structure.

Although the cathode contains organic liquid electrolyte, the overallvolume of liquid in the solid-state cell is about 10% of that in astandard LIB. This reduction of liquid greatly reduces the explosion andfire potential of the solid-state cell 100 compared to a standard LIB.

While some embodiments have been shown and described, it will be obviousto those skilled in the relevant arts that changes and modifications maybe made without departing from the invention in its broader aspects.Therefore, the aim in the appended claims is to cover all such changesand modifications that fall within the true spirit and scope of theinvention. The matter set forth in the foregoing description andaccompanying drawings is offered by way of illustration only and not asa limitation. The actual scope of the invention is intended to bedefined in the following claims when viewed in their proper perspectivebased on the prior art.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to limit the invention. As usedherein, the singular forms “a,” “an,” and “the” are intended to includethe plural forms as well, unless the context clearly indicatesotherwise. Furthermore, to the extent that the terms “including,”“includes,” “having,” “has,” “with,” or variants thereof are used ineither the detailed description and/or the claims, such terms areintended to be inclusive in a manner similar to the term “comprising.”

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which this invention belongs.Furthermore, terms, such as those defined in commonly used dictionaries,should be interpreted as having a meaning that is consistent with theirmeaning in the context of the relevant art, and will not be interpretedin an idealized or overly formal sense unless expressly so definedherein.

What is claimed is:
 1. A monolithic ceramic electrochemical cellcomprising: a first electrochemical sub cell housing comprising a firstanode receptive space, a cathode receptive space, a first separatorbetween the first anode receptive space and the cathode receptive space;and a second electrochemical sub cell housing comprising a second anodereceptive space, the cathode receptive space, and a second separatorbetween the second anode receptive space and the cathode receptivespace, the cathode receptive space being the cathode receptive space forthe first electrochemical sub-cell housing and the secondelectrochemical sub-cell housing, wherein the cathode receptive space isbounded on at least one side by a cathode current collector, the cathodecurrent collector including: one selected from the group consisting of ametal, a metal alloy, a conductive ceramic, and a conductive carbonbased material; and an ion conducting material to conduct the intendedcharge transfer ion of the specific battery design.
 2. The monolithicceramic electrochemical cell of claim 1, wherein the ion conductingmaterial comprises lithium lanthanum zirconate.
 3. The monolithicceramic electrochemical cell of claim 2, wherein the cathode currentcollector comprises a porous film that forms an electronic percolatingnetwork through the plane of the cathode current collectors.
 4. Themonolithic ceramic electrochemical cell of claim 1, wherein the metal,metal alloy, conductive ceramic or conducting carbon material comprisesbetween 20% and 99% by volume of the cathode current collector.
 5. Themonolithic ceramic electrochemical cell of claim 1, wherein the cathodereceptive space is bounded on one side by a first cathode currentcollector and on the other side by a second cathode current collector.6. The monolithic ceramic electrochemical cell of claim 5, wherein thefirst electrochemical sub cell housing comprises the first cathodecurrent collector and wherein the second electrochemical cell housingcomprises the second cathode current collector.
 7. The monolithicceramic electrochemical cell of claim 1, wherein the cathode receptivespace comprises a filling aperture configured to contain catholyte, thefilling aperture including a seal and wherein the seal is configured toisolate the catholyte and provide pressure relief from the cathodereceptive space.
 8. The monolithic ceramic electrochemical cell of claim1, wherein the first electrochemical cell sub cell housing comprises afirst plurality of integrated electron conductive circuits and whereinthe second electrochemical sub cell housing comprises a second pluralityof integrated electron conductive circuits.
 9. The monolithic ceramicelectrochemical cell of claim 8, wherein the first and second pluralityof integrated electron conductive circuits each comprise an anodecurrent collector and a cathode current collector.
 10. The monolithicceramic electrochemical cell of claim 1, wherein the anode receptivespaces are configured as hermetically sealed volumes, partially filledwith a solid-state electrolyte.
 11. The monolithic ceramicelectrochemical cell of claim 10, wherein the solid-state electrolytecomprises a ceramic.
 12. The monolithic ceramic electrochemical cell ofclaim 11, wherein the ceramic is selected from a group consisting of:sulfides, borides, carbides, nitrides, phosphides, oxides, selenides,fluorides, chlorides, bromides, iodides, and combinations thereof. 13.The monolithic ceramic electrochemical cell of claim 11, wherein thesolid-state electrolyte forms a network of continuous ionic conductivitybetween the separator and a first anode current collector and a secondanode current collector.
 14. The monolithic ceramic electrochemical cellof claim 11, wherein the solid-state electrolyte occupies between 20%and 80% volume of the first and second anode receptive spaces.
 15. Themonolithic ceramic electrochemical cell of claim 9, wherein the anodecurrent collector serves as a current collector for the first anodereceptive spaces of the first electrochemical sub cell housing and thecurrent collector for the second anode receptive spaces of the secondelectrochemical sub cell housing.
 16. The monolithic ceramicelectrochemical cell of claim 1, wherein the cathode receptive space ispartially filled with strands of ceramic material between 1% and 60%volume.
 17. The monolithic ceramic electrochemical cell of claim 1,further comprising insulating material between the first electrochemicalsub cell housing and the second electrochemical sub cell housing. 18.The monolithic ceramic electrochemical cell of claim 1, wherein thefirst and second anode receptive spaces are sealed and the cathodereceptive space is partially.